Catalyst for ester hydrogenation

ABSTRACT

A process for hydrogenation of esters to alcohols which comprises contacting the ester with hydrogen and a catalyst comprising cobalt, zinc and copper under catalytic hydrogenation conditions including a temperature between 150° and 450° C and a pressure of 500-10,000 psig.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. application Ser. No. 711,909, filed Aug. 5, 1976, now abandoned which in turn is a continuation-in-part of U.S. Application Ser. No. 578,799, filed May 19, 1975, now abandoned.

BACKGROUND OF THE INVENTION

The present invention relates to the hydrogenation of esters to alchols using a solid hydrogenation catalyst.

The hydrogenation of esters to alcohols is well known. See, for example, U.S. Pat. No. 1,605,093 disclosing the following ester hydrogenation reaction:

    R.COO.R' + 2H.sub.2 = R.CH.sub.2 OH + R'.OH

according to the 1,605,093 patent, a copper catalyst is used in the ester hydrogenation.

It is frequently stated that the best method of converting an acid to the corresponding alcohol usually involves proceeding through the ester. Esters are normally obtained from acids in nearly quantitative yields, and the esters can be reduced to alcohols, usually with considerably higher yields than in reducing the corresponding acid to the alcohol. Esters have been reduced using various means such as lithium aluminum hydride, sodium plus an alcohol, or a solid hydrogenation catalyst. These methods are indicated in general by the equations below: ##STR1##

Besides copper chromite as an ester hydrogenation catalyst, as indicated in the last equation above, other hydrogenation catalysts, such as the copper chromite/barium catalyst in U.S. Pat. No. 2,091,800 to Homer Adkins et al, have been disclosed.

U.S. Pat. No. 2,093,159 discloses a

"process for the catalytic hydrogenation of esters of aliphatic alkylmonocarboxylic acids, which comprises passing the said esters together with hydrogen while heating to a temperature of the range from 200° to 400° C. over a hydrogenating catalyst essentially comprising cobalt in combination with an activating substance, selected from the class consisting of oxides of metals giving acids with oxygen and compounds of alkali, alkaline earth and rare earth metals with metal acids until substantial quantities of alcohols corresponding to the said alkylmonocarboxylic acid radicles are formed."

According to the disclosure of U.S. Pat. No. 2,093,159,

"Suitable catalytic substances are for example copper, nickel, silver, zinc, cadmium, lead or cobalt or mixtures thereof and they may be prepared from their salts, oxides or other compounds prior to or after an incorporation with activating substances. The activating substances may be chosen from compounds of the metals giving acids with oxygen, such as chromium, molybdenum, tungsten, uranium, manganese, vanadium or titanium or mixtures thereof as well as from compounds of the alkali, alkali earth or rare earth metals."

U.S. Pat. No. 2,109,844 teaches away from the use of cobalt-containing catalysts in converting esters to alcohols. At page 5 the 2,109,844 patent states:

". . . if the hydrogenation of a fatty glyceride is to be operated for the production of alcohols and esters to the substantial exclusion of hydrocarbons it is preferable to select as the catalyst a composition comprising a member of the group of nonferrous hydrogenating metals such as copper, tin, silver, cadmium, zinc, lead, their oxides and chromites, and oxides of manganese and magnesium. Especially good results are obtained with finely divided copper oxide, either wholly or partially reduced and preferably supported upon an inert surface-extending material such as kieselguhr, or promoted by such oxide promoters as manganese oxide, zinc oxide, magnesium oxide, or chromium oxide. The above mentioned mild-acting catalysts may be termed the alcohol-forming catalysts to distinguish them from the more energetic ferrous metal groups. Elementary nickel, cobalt, and iron when suitably supported on kieselguhr may be used to effect the reduction of fatty glycerides with hydrogen, but in these cases the product contains besides alcohols and waxes a preponderance of hydrocarbons, and this disadvantage in most cases will prove so serious as to preclude the use of these catalysts unless the hydrocarbons themselves are the desired end products." Other patents which disclose catalysts for hydrogenation of esters and carboxylic acids include U.S. Pat. Nos. 2,110,843; 2,118,007; 2,121,367; 2,782,243; 3,173,959 (copper-zinc chromite catalyst for ester reduction); 3,267,157 (activated copper chromite catalyst for acid and ester hydrogenation).

U.S. Pat. No. 2,285,448 discloses hydrogenation of glycolic acid and its esters to obtain ethylene glycol. According to the 2,285,448 patent, a copper-magnesium catalyst is preferred. At column 2, line 46 of the 2,285,448 patent it is stated that:

"In place of magnesium oxide, other metal oxides which promote the activity of the copper oxide may be employed such, for example, as an oxide of nickel, iron, cobalt, manganese, chromium, calcium, barium, strontium, potassium, caesium, zinc, cadmium and silver, or mixtures thereof."

SUMMARY OF THE INVENTION

According to the present invention a process is provided for hydrogenation of carboxylic acid esters to alcohols, which process comprises contacting the ester with hydrogen gas and a catalyst comprising cobalt, zinc and copper under catalytic hydrogenation conditions including a temperature between 150° and 450° C. and pressures of 500 to 10,000 psi. This may be either a liquid or vapor phase process, preferably liquid phase.

Among other factors, the present invention is based on my finding that the cobalt-zinc-copper catalyst is a highly effective ester hydrogenation catalyst in terms of activity, selectivity, and stability. The high stability of the catalyst is particularly surprising since catalytically active cupric oxide would be expected to be reduced to inactive copper metal under the hydrogenation conditions. In Organic Reactions, vol. VIII (1954), published by John Wiley & Sons, New York, on page 8 concerning copper chromite Adkins states:

"The catalyst is inactivated if, through excessive temperatures in the preparation or use of the catalyst, the cupric oxide reacts with cupric chromite to give cuprous chromite, Cu₂ Cr₂ O₄, and oxygen. However, the most frequent cause of inactivation of the catalyst is the reduction of the cupric oxide to copper. This is evidenced by a change in the color of the catalyst from black to a copper red. Such a deactivation of the catalyst is favored by the presence of water, acids, or ammonia in the reaction mixture. The reduction and inactivation of the catalyst may be minimized by precipitating barium (or strontium or calcium) chromate along with the basic copper ammonium chromate in the first step in the preparation of the catalyst."

In agreement with Adkins, I frequently find that the less stable catalysts turn "copper red" with use while the more stable catalysts remain gray to black.

According to preferred embodiments of the present invention, the ester feedstock is a polyglycolide H(C₂ H₂ O₂)nOH derived from glycolic acid, dialkyl oxalate, aliphatic monocarboxylic acid ester, aliphatic dicarboxylic acid diester, or alpha-hydroxy mono-carboxylic aliphatic acid ester. The term aliphatic is used to include alicyclic.

For the aliphatic acid esters, preferably the aliphatic groups are C₂ (including acetates) to C₃₀ and preferably they are saturated. The aliphatic groups may be both acyclic and cyclic. The other moiety of the ester (alcohol-derived moiety) is preferably a C₁ to C₂₀ alkyl group or alkyl hydroxy group such as from ethylene glycol. By the term "alcohol-derived moiety" is meant the group attached by ether linkage to the carbonyl group of the ester.

Preferred dialkyl oxalate ester feedstocks are those wherein the alkyl groups are C₁ to C₂₀, more preferably C₁ to C₄. Hydrogenation of the dialkyl oxalate yields ethylene glycol and alkyl monools.

Preferred aliphatic carboxylic acid ester feeds are of the formula ##STR2## wherein R¹ and R² are C₁ to C₂₀ alkyl groups, n = 0 or 1 and A is an alkylene group of 1 to 10 carbon atoms which may be branched chain, and preferably is saturated with hydrogen.

The term "carboxylic acid esters" is used herein in the sense of esters composed of carbon, hydrogen, and oxygen and preferably not containing any halogen, sulfur or nitrogen -- that is, at least no halogen, sulfur, or nitrogen or the like in an active form or degradable form such that the ester hydrogenation reaction is substantially prevented.

The most preferred feeds for the process of the present invention are ethylene glycol glycolate, diethylene glycol glycolate, and polyglycolides (typically the polyglycolide feeds are in the form of an alkyl glycolate obtained from the polyglycolide and solvent alcohol).

The ethylene glycol glycolate can be obtained from glycolic acid by reaction of ethylene glycol with glycolic acid or its oligomers under usual esterification conditions. Likewise, the diethylene glycol glycolate can be obtained by reaction of glycolic acid or its oligomers with diethylene glycol. Both the monoglycolates and the bisglycolates of these glycol solvents, i.e., ethylene glycol and diethylene glycol, can be hydrogenated in the present process.

Polyglycolide can be obtained by dehydrating glycolic acid, for example by heating glycolic acid under vacuum and removing water. Preferably the process of the present invention is carried out in the presence of an alcohol solvent for the ester feed so that in the case of the polyglycolide feed the polyglycolide would be in the form of the ester resulting from the reaction of the alcohol solvent with the polyglycolide. Polyglycolide reacts with alcohols to form esters with less formation of water than would be the case in reacting glycolic acid directly with an alcohol. The general reaction for the polyglycolide with an alcohol solvent to form a glycolate is as follows: ##STR3## Thus in the case of n=5 there would be 5 mols of the glycolate for one mol of water.

Preferred solvents for the ester hydrogenation process of the present invention are C₁ -C₂₀ alkyl alcohols. Ethylene glycol and diethylene glycol are especially preferred solvents. Lower alcohols such as methanol, ethanol, and propanol and butyl alcohols are also advantageous solvents. Preferred amounts of the alcohol solvent are 0.1-10 parts per one part ester feed by weight, more preferably 0.5-3 parts per one part ester feed. Preferably the alcohol solvent is not an unsaturated alcohol nor an aromatic alcohol.

Although the reaction of the present invention has been carried out in mixed liquid-vapor phase, generally it is preferred to carry out the reaction with the ester and the alcohol solvent in the liquid phase. Typically the hydrogen remains in gaseous phase except for dissolved hydrogen.

Suitable pressures are between about 500 to 10,000 psig, preferably between 1,000 and 5,000 psig. Preferred hydrogenation reaction temperatures are 100° to 350° C., more preferably 180°-250° C. Suitable hydrogen to ester molar ratios are between 1.1/1 and 100/1, and preferably between 1.5/1 and 10/1. Suitable liquid hourly space velocities for the ester feed over the catalyst are between 0.1 and 100 and preferably are between 0.5 and 10.

The cobalt, zinc and copper components of the catalyst can be present in the catalyst in elemental form or in compound form, such as in the oxide form. In the fresh catalyst the components are present in compound form as in the oxide, hydroxide, carbonate or complex salt. Under hydrogenation conditions or after use, the components may be partly or largely in elemental form. For example, cobalt may be reduced to the elemental form while copper and zinc remain mostly in compound form, particularly as the oxide. Preferred amounts of the cobalt, zinc and copper for the catalyst are between 10 and 50 weight percent cobalt, 10 and 50 weight percent zinc, and 1 and 50 weight percent copper, and particularly preferred amounts are between 15 and 40 weight percent cobalt, 15 and 40 weight percent zinc, and 1 and 40 weight percent copper.

The catalyst can be used in unsupported form or in supported form. When used in supported form, the weight percent of the support as, for example, alumina, silica, charcoal, or other porous support, can be between about 50 and 98 weight percent of the catalyst with the cobalt, zinc and copper components being disposed on the support in weight amounts as previously given, correspondingly reduced in view of the weight percent of the catalyst support.

The catalyst used in the present invention must contain cobalt, zinc and copper but in addition to support material for the catalyst other materials may be included in the catalyst so long as they do not block the effectiveness of the catalyst. As shown by the examples hereinbelow, nickel may be added to the cobalt-zinc-copper catalyst.

EXAMPLE I

Typically the catalytic solids are prepared by precipitation from aqueous solution using an aqueous solution of base as the precipitating agent. The precipitated solids are isolated, washed, dried and calcined before use. The following is a typical preparation of a coprecipitated cobalt-zinc-copper oxide catalyst.

A solution of 30g (0.1 mole) Co(NO₃)₂.6H₂ O, 30g (0.1 mole) Zn(NO₃)₂.6H₂ O and 24g (0.1 mole) Cu(NO₃)₂.3H₂ O in 500 ml of distilled water is added dropwise with stirring to a solution of 40g (0.42) (NH₄)₂ CO₃ in 400 ml of distilled water. The precipitate is recovered by filtration and washed four times with 500 ml portions of distilled water. The wet solid is dried overnight in a vacuum oven (typically 80° C., 200-500 mm Hg) and calcined in air for 4 hours at 100° C., 4 hours at 200° C. and for 16-20 hours at 500° C. The yield of catalyst powder is 20-25g. A fresh catalyst prepared in this way had a surface area of 55 m² /g.

The separately precipitated metal salts and other combinations of the metal oxides were also prepared in this way.

EXAMPLE II

An effective catalyst can also be prepared in the following manner. A solution of 22g (0.1 mole) Zn(OAc)₂.2H₂ O, 25 g (0.1 mole) Co(OAc)₂.4H₂ O and 20g (0.1 mole) Cu(OAc)₂.H₂ O in 500 ml of distilled water is stirred while a solution of 40g (0.42 mole) (NH₄)₂ CO₃ in 400 ml of distilled water is added. The precipitate is isolated by filtration, washed with distilled water and dried overnight in a vacuum oven. The dried catalyst is calcined 2 hours at 100° C., 2 hours at 200° C. and for 16-20 hours at 250° C. The yield is 25-30g of catalyst powder. A fresh catalyst prepared in this way had a surface area of 139 m² /g.

Examples I and II illustrate typical methods used to prepare the hydrogenation catalysts effective in the invention. In both examples, the catalyst was washed, dried, and calcined prior to use. It has been found that the calcination step is particularly important when hydrogenating concentrated solutions of glycol glycolate. Significant amounts of metals, especially zinc, are lost during the hydrogenation reaction unless the final calcination is carried out at temperatures above 300° C. This can lead to catalyst deterioration in long-term hydrogenation runs. Accordingly, in a preferred method of preparation, the dried catalyst is calcined by heating at a temperature of from about 200° C. to about 300° C. until carbonates and hydrates are substantially completely decomposed and then heated at a temperature of from about 400° C. to about 500° C. for 0.5 to 16 hours or more. In a preferred method, the catalyst is calcined by heating at about 250° C. for about 2 hours and then at about 450° C. for about 16 hours. The following Table illustrates the relative stability of catalysts calcined above 300° C. compared to catalysts calcined at 300° C. and 250° C. in the hydrogenation of glycol glycolate solutions. As can be seen, the hydrogenated glycol product obtained using the three low temperature catalysts contained significant amounts of zinc, indicating catalyst decomposition.

    ______________________________________                                         Calcination, ° C.                                                                       Zinc ppm in Product                                            ______________________________________                                         300             42                                                             250             16                                                             250             20                                                             450             0.6                                                            450             1.0                                                            450             0                                                              ______________________________________                                    

EXAMPLE III

for the hydrogenations, polyglycolide was prepared from commercially available aqueous glycolic acid (70% solution) by vacuum distillation removal of most of the water. The equivalent weight of the polyglycolide was determined by saponification and titration. Hydrogenations were carried out on mixtures of 7g polyglycolide and 60g of methanol in a rocking autoclave. Product analyses were by vapor phase chromatography using an internal standard.

Several commercially available copper chromite ester hydrogenation catalysts were tested. The following results were obtained using 5g of catalyst at 250° C. and 3000-3500 psig for 8 hours. The best of these,

    ______________________________________                                         Copper Chromite Conversion to                                                  Catalyst        Ethylene Glycol                                                ______________________________________                                         Harshaw Cu1110-P                                                                               27%                                                            Calsicat* 102   25%                                                            Harshaw Cu0401-P                                                                               51%                                                            Calsicat* 101   81%                                                            Calsicat* 104   90%                                                            ______________________________________                                          *Calsicat is a Division of the Mallinckrodt Chemical Works.              

Calsicat 104, was compared with the metal oxides prepared according to Example I. These hydrogenations were carried out for 1 hour at 250° C. on 7g polyglycolide in 60g of methanol. These results demonstrate that the coprecipitated cobalt-zinc-copper oxide catalyst (I) is superior to the commercial copper chromites, the individual oxides, and to the coprecipitated cobalt-zinc oxide for this hydrogenation.

    ______________________________________                                                   Wt. of    Pressure, Conversion to                                    Catalyst  Catalyst  psig      Ethylene Glycol                                  ______________________________________                                         Calsicat 104                                                                             5g        3450      79%                                              Co-Zn-Cu                                                                       Oxides (I)                                                                               5g        2450      82%                                              Co-Zn Oxides                                                                             5g        2560      32%                                              Cu Oxide  2.5g      2250      42%                                              Zn Oxide  2.5g      2650       0%                                              Co Oxide  2.5g      2650       0%                                              ______________________________________                                    

EXAMPLE IV

Comparisons were also made in a stirred autoclave at 250° C. using 7g polyglycolide (prepared as in Example III), 60g ethanol, and 5g catalyst. These results show that I is superior to the commercial copper chromite and to the coprecipitated cobalt-copper oxides. The coprecipitated copper-zinc oxide is equal to I in this test but further work shows I to be more stable. The results also show that a physical mixture of the separately prepared metal oxides (hereinafter referred to as: I, physical mixture) with the same composition as I is an effective catalyst.

    ______________________________________                                                                    Conversion to                                       Catalyst Pressure  Time    Ethylene Glycol                                     ______________________________________                                         Calsicat 104                                                                            3550 psig   2 hrs 80%                                                  I       2700 psig 0.5 hr  90%                                                 Co-Cu Oxides                                                                            2800 psig   1 hr  42%                                                 Cu-Zn Oxides                                                                            3200 psig 0.5 hr  90%                                                 I, physical                                                                             3100 psig 0.5 hr  87%                                                  mixture                                                                       ______________________________________                                    

EXAMPLE V

Catalyst stability comparisons were carried out by recycling recovered used catalysts with fresh feed. In each cycle 7g polyglycolide (prepard as in Example III) and 60g of solvent were used. In each case there was 5g of fresh catalyst in the first cycle. Hydrogenations were run for 30 min at 250° C. and 2800-3100 psig.

    ______________________________________                                                                     Conversion to                                      Catalyst  Solvent  Cycle(s) Ethylene Glycol                                    ______________________________________                                         I         ethanol  1-4      90%                                                Cu-Zn oxides                                                                             ethanol  1        90%                                                Cu-Zn oxides                                                                             ethanol  2        82%                                                Cu-Zn oxides                                                                             ethanol  3        62%                                                I, (physical                                                                             methanol 1        87%                                                 mixture)                                                                      I, (physical                                                                             methanol 2        83%                                                 mixture)                                                                      I, (physical                                                                             methanol 3        82%                                                 mixture)                                                                      I, (physical                                                                             methanol 4        45%                                                 mixture)                                                                      ______________________________________                                    

Both I and I (physical mixture) show greater stability than the coprecipitated Cu-Zn oxides.

EXAMPLE VI

Coprecipitated cobalt-zinc-copper oxide catalysts with lower levels of copper were prepared according to the procedure of Example I. The following results were obtained in a rocking autoclave using 7g polyglycolide (prepared as in Example III), 60g methanol and 5g catalyst at 250° C. and 2500 psig for 1 hour. These results demonstrate that even very small amounts of copper have a favorable effect on catalyst performance. However, I have found that copper concentrations above about 0.1 g-atom per g atom of cobalt are preferred for the process of the present invention. Preferably about 0.3 to 2.0g atoms of zinc and 0.1 to 2.0 g-atoms of copper are used in the catalyst per g atom of cobalt.

    ______________________________________                                                                 Conversion to                                          Catalyst    Atom Ratio  Ethylene Glycol                                        ______________________________________                                         Co-Zn-oxides                                                                               Co/Zn = 1/1 32%                                                    Co-Zn-Cu oxides                                                                            Co/Zn/Cu =                                                                     1/1/0.1     67%                                                    Co-Zn-Cu oxides                                                                            Co/Zn/Cu =                                                                     1/1/0.2 84%                                                        ______________________________________                                    

EXAMPLE VII

In another comparison polyglycolide (prepared as in Example III) was esterified with methanol prior to hydrogenation. In these cases 7g polyglycolide was reacted with 60g of methanol for 30 min at 200° C. This procedure converted about 90% of the polyglycolide to methyl glycolate. Catalyst was added and the hydrogenation was carried out at 250° C. and 2700 psig for 30 min. Only 0.5g of catalyst was used.

    ______________________________________                                                         Conversion to                                                  Catalyst        Ethylene Glycol                                                ______________________________________                                         Calsicat 104    11%                                                             I              63%                                                            II (Example II) 77%                                                            Calsicat 101    3.2%                                                           Harshaw Cu0401P 2.3%                                                           ______________________________________                                    

Both I and II (coprecipitated Co-Cu-Zn oxides from Example II) are far superior to the commercial catalysts.

EXAMPLE VIII

The above results were obtained using methyl glycolate prepared directly from polyglycolide. These mixtures contain small amounts of impurities such as water and unmethylated glycolates which could affect catalyst performance. Therefore, comparisons were made with distilled 99.6% methyl glycolate. These runs were in a rocking autoclave with 10g of methylglycolate, 60g of methanol and only 0.1g of catalyst at 250° C. and 2800 psig for 2.5 hours.

    ______________________________________                                                         Conversion to                                                  Catalyst        Ethylene Glycol                                                ______________________________________                                         Calsicat 104    30%                                                             I              89%                                                             II             76%                                                            II (Co/Zn/Cu = 1/1/2)                                                                          63%                                                            II (Co/Zn/Cu - 1/1/0.5)                                                                        58%                                                            Cu-Zn oxides    30%                                                            ______________________________________                                    

With these high substrate to catalyst ratios and pure methyl glycolate the results again show I and II to be superior to a good commercial copper chromite (and to the Cu-Zu oxides prepared according to Example I). Also catalysts prepared according to Example II with Co/Zn/Cu ratios of 1/1/2 and 1/1/0.5 were effective catalysts.

EXAMPLE IX

Ethyl laurate (22.8g) was hydrogenated in a stirred autoclave for 4 hours at 250° C. and 3000 psig with 60g ethanol and 5g of catalyst. Saponification-titration analysis showed 73% conversion with Calsicat 104 and 86% conversion with I. Chromatographic analysis showed the presence of 1-dodecanol.

EXAMPLE X

Diethyloxalate (17.5g) was hydrogenated in a stirred autoclave for 1 hour at 250° C. and 3400 psig with 60g of ethanol and 5g of catalyst. Calsicat 104 converted 58% of the diethyloxalate to ethylene glycol compared to 72% with I.

EXAMPLE XI

Polyglycolide was esterified with diethylene glycol to obtain diethylene glycol glycolate as the feed to the ester hydrogenation step. The saponification equivalent was 516g or 32% ester concentration calculated as diethylene glycol glycolate. An 80g portion of this solution was hydrogenated in a rocking autoclave at 225° C./1500 psig for 6 hours using 0.5g of catalyst prepared according to Example I. The conversion to ethylene glycol was 77%. The ethylene glycol productivity was 2.5g per g of catalyst each hour.

EXAMPLE XII

A solution of 50% diethylene glycol glycolate in diethylene glycol was hydrogenated as in Example XI. The conversion was 57% to ethylene glycol or a productivity of 2.6g per g of catalyst each hour.

EXAMPLE XIII

Catalysts prepared according to Examples I and II were tabletted with sodium meta silicate binder and broken into 20-28 mesh particles. These particles were used to hydrogenate ethylene glycol glycolate/ethylene glycol and diethylene glycolate/diethylene glycol.

    ______________________________________                                                            Conversion to                                                                               Glycol                                         Catalyst                                                                              Feed        Ethylene Glycol                                                                             Productivity                                   ______________________________________                                         I-pellets                                                                             diethylene                                                                     glycol glycolate                                                                           38%          1.1g/gcat,hr                                   II-pellets                                                                            diethylene                                                                     glycol glycolate                                                                           80%          2.3g/gcat,hr                                   II-pellets                                                                            ethylene                                                                       glycol glycolate                                                                           39%          1.3g/gcat,hr                                   ______________________________________                                    

EXAMPLE XIV

A catalyst prepared as in Example II, except that the metal acetate solution was added to the ammonium carbonate solution, was used to hydrogenate a 52% solution of ethylene glycol glycolate in ethylene glycol in a stirred autoclave at 225° C. and 1500 psig. The rate of glycolate conversion was 0.03 mole per g of catalyst each hour.

EXAMPLE XV

A catalyst was prepared as in Example XIV except that the acetate solution also included 0.01 mole of nickel acetate. The finished catalyst was used to hydrogenate ethylene glycol glycolate as in Example XIV. The rate of glycolate conversion was 0.02 mole per g of catalyst each hour. This demonstrates that including nickel in the catalyst still gives an effective hydrogenation catalyst. 

What is claimed is:
 1. A catalyst suitable for use in the hydrogenation of carboxylic acid esters the metal components of which are not fused and consist essentially of the elemental, oxide, hydroxide, or carbonate form of cobalt, zinc, and copper.
 2. A catalyst in accordance with claim 1 which is prepared by a method comprising the steps of: (1) forming an aqueous solution of the soluble salts of the metal components, (2) treating the solution with an aqueous solution of a basic precipitating agent, (3) isolating the precipitated solids, (4) drying the solids, and (5) calcining the dried solids at a temperature above 300° C.
 3. A catalyst in accordance with claim 2 which is calcined by heating at a temperature of from about 200° C. to about 300° C. until carbonates and hydrates are substantially decomposed, and then heated at a temperature of from about 400° C. to about 500° C. for at least 0.5 hours.
 4. A catalyst in accordance with claim 3 calcined by heating at about 250° C. for about 2 hours and then at about 450° C. for about 16 hours.
 5. A catalyst in accordance with claim 1 wherein the metal components are in the elemental or oxide form.
 6. A catalyst in accordance with claim 1 wherein the cobalt component is present in an amount ranging from 10 to 50 weight percent of the catalyst, the zinc component is present in an amount ranging from 10 to 50 weight percent of the catalyst, and the copper component is present in an amount ranging from 1 to 50 weight percent of the catalyst; said weight percentages being based upon the weight of the catalyst in unsupported form.
 7. A catalyst in accordance with claim 6 wherein the cobalt component and the zinc component are each present in an amount ranging from 15 to 40 weight percent of the catalyst, and the copper component is present in an amount ranging from 1 to 40 weight percent of the catalyst.
 8. A catalyst in accordance with claim 1 wherein for each gram atom of cobalt there is present from about 0.3 to 2.0 gram atom of zinc and from about 0.1 to 2.0 gram atoms of copper.
 9. A catalyst in accordance with claim 1 containing a minor amount of nickel. 